CN102604188A - Antioxidant cross-linked polymer and preparation method thereof - Google Patents
Antioxidant cross-linked polymer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an antioxidant cross-linked polymer and a preparation method thereof. The existing cross-linked ultra-high molecular weight polyethylene has relatively low strength and toughness. The polymer provided by the invention is a mixture of cross-linked ultra-high molecular weight polyethylene and an antioxidant at a weight ratio of (100-10000):1. The preparation method comprises the following steps of: dissolving the antioxidant into an organic solvent, adding the ultra-high molecular weight polyethylene resin powder, sufficiently mixing and drying; placing the mixture powder into a mould; heating and pressurizing so as to melt the mixture powder into block; cooling the block below the melting point and annealing while maintaining the pressure; reducing the temperature to normal temperature and demoulding to obtain block blank; and irradiating with high-power electron beam to obtain the product. The polyethylene material provided by the invention has excellent wear resistance, oxidation stability, tensile strength and impact strength, is suitable for manufacturing the friction lining of an artificial joint, and can reduce the wear of the artificial joint.
Description
Technical field
The present invention relates to a kind of anti-oxidant cross-linked polymer and preparation method thereof, this polymkeric substance is applicable to that body is implanted into medicine equipment, has excellent oxidation stability, belongs to the materialogy technical field.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) is because its excellent abrasive, good mechanical performance and biocompatibility begin to be used for the stressed material of joint prosthesis liner the sixties in last century.Yet, the ultrahigh molecular weight polyethylene(UHMWPE) prosthetic element in vivo in the practical application because the long service wearing and tearing produce and take measurements greatly at the abrasive dust below several microns, and these abrasive dusts cause the dissolving of prosthese Peripheral Bone easily, thereby cause aseptic looseningly, cause joint prosthesis to lose efficacy.
The nineties in last century, people adopt irradiation crosslinking technological to improve the antiwear property of ultrahigh molecular weight polyethylene(UHMWPE).Yet the tired toughness and the shock resistance of ultrahigh molecular weight polyethylene(UHMWPE) significantly descend after the cross-linking radiation; In addition, the radical that irradiation produces long period in the ultrahigh molecular weight polyethylene(UHMWPE) lattice exists, and is prone to react with oxygen; Cause material to be the waterfall type oxidation; Finally make the material molecule splitting of chain, physical and mechanical properties descends, and the Vilaterm prosthese finally becomes fragile and lost efficacy.
U.S. Pat 6641617 B1 disclose the method for melting recrystallization behind a kind of irradiation: the ultrahigh molecular weight polyethylene(UHMWPE) behind the irradiation is heated to more than the fusing point; With the fusion of ultrahigh molecular weight polyethylene(UHMWPE) crystal, can free-radical contents residual in the ultrahigh molecular weight polyethylene(UHMWPE) be reduced to below the detectability of electron spin resonance spectrometer.Then, the fused polymkeric substance is slowly cooled to room temperature, the polymkeric substance recrystallize obtains crosslinked and non-oxidizing basically polymkeric substance.The wear rate of the polymkeric substance that obtains like this is lower than the wear rate of uncrosslinked ultrahigh molecular weight polyethylene(UHMWPE), and wear rate reduces along with the increase of irradiation dose.Cross-linking radiation and follow-up melting recrystallization make the crystalline structure of polymkeric substance that change take place, and crystallinity of polymer reduces, and fusing point reduces; The thickness attenuation of platelet; Cross-linking radiation and follow-up melting recrystallization also make the tensile strength of polymkeric substance reduce, and elongation at break reduces, and tired toughness descends; Shock strength reduces, and the application in joint prosthesis causes detrimentally affect to polymkeric substance.
U.S. Pat 6562540 B2 disclose a kind of method of postirradiation annealing recrystallize: the ultrahigh molecular weight polyethylene(UHMWPE) behind the irradiation is heated to the temperature that still is lower than fusing point near fusing point; Keep (annealing) after for some time, can significantly reduce the free-radical contents in the ultrahigh molecular weight polyethylene(UHMWPE).Then, the polymkeric substance of heat is slowly cooled to room temperature, obtain crosslinked and polymkeric substance that have certain resistance of oxidation.The wear rate of the polymkeric substance that obtains like this is lower than the wear rate of uncrosslinked ultrahigh molecular weight polyethylene(UHMWPE), and wear rate reduces along with the increase of irradiation dose.Because annealing process does not have the completely destroy crystalline structure, has kept most crystal basically, therefore; After the cooling, the physical and mechanical properties of crosslinked ultra-high-molecular-weight polyethylene has obtained keeping the tensile strength of material preferably; Shock strength, tired toughness are all near the level before the annealing.Yet,, therefore in material, still have residual radical because annealing process is not destroyed crystal; In vivo during life-time service; These radicals can cause material slow oxidation (UHMWPE Biomaterials Handbook (Second Edition), 2009, Pages 205-219).
U.S. Pat 2007/0059334 A1 discloses a kind of ultrahigh molecular weight polyethylene(UHMWPE) that contains inhibitor; Behind this polymkeric substance cross-linking radiation, inhibitor wherein can be caught the also residual radical of constant illumination generation, thereby has significantly improved the oxidative stability of crosslinked polyethylene; Behind the cross-linking radiation; Need not carry out any thermal treatment, can obtain having cross-linked polymer, avoid thermal treatment to cause material mechanical performance further to descend than the strong anti-oxidation ability.In this patent, described inhibitor mainly is meant vitamin E (Viteolin).Its cardinal principle is, vitamin E is when running into radical, and the proton on its phenolic hydroxyl group is prone to and combined with radical, obtains the phenol oxyradical, and the phenol oxyradical forms conjugated system with phenyl ring, and free radical reaction is active to be reduced, the stability raising.
Oral etc. (Biomaterials, 2008,29:3557) reported that vitamin E is inhibited to the cross-linking radiation of ultrahigh molecular weight polyethylene(UHMWPE).When the content of vitamin E in the ultrahigh molecular weight polyethylene(UHMWPE) is higher (as being higher than 0.1 wt% weight percent), vitamin E can be rapidly and the radical in the polyolefine react, thereby hinder the compound and crosslinking reaction between the radical in the polymkeric substance.Like this, vitamin E has not only suppressed the generation of crosslinking structure, has also promoted the molecule chain break simultaneously, has reduced molecular weight.Therefore, high-load vitamin E is not only bad for improving degree of crosslinking and abrasion resistance properties, and can reduce the mechanical property of material.
On the other hand, if during the content of vitamin E lower (as being lower than 0.05wt%), vitamin E receives the energetic ray bombardment, can lose anti-oxidant activity, thereby partly lose resistance of oxidation.
U.S. Pat 2004/0156879 A1 discloses a kind of method of in crosslinked ultra-high-molecular-weight polyethylene, introducing vitamin E: the ultrahigh molecular weight polyethylene(UHMWPE) behind the cross-linking radiation is immersed in the vitamin E; About 120 ℃, make vitamin E be diffused into polyethylene surface; After taking out polymkeric substance; Wipe the vitamin E of surface adhesion, kept 2-72 hour down at 120 ℃ then, make vitamin E further to the Vilaterm internal divergence to being evenly distributed.
U.S. Pat 7431874 B2 also disclose another kind of method; Be about to ultrahigh molecular weight polyethylene and become prosthese blank (preform); Behind the cross-linking radiation, immerse in the vitamin E of heat, after the taking-up; Remove the vitamin E of surface attachment, further thermal treatment makes vitamin E diffuse to prosthese blank inside up to uniform distribution.At last the prosthese blank is cut into final prosthese.
Adopt the method for irradiation-immersion-diffusion, length consuming time, thermal treatment also possibly cause material and prosthese character further to descend, and the prosthese distortion is difficult to realize vitamin E real uniform distribution in prosthese.
U.S. Pat 2008/0293856 A1 discloses many phenolic acids organism as the polyolefine inhibitor, but problem such as the activity that does not relate to polyolefine cross-linking radiation and inhibitor and inhibition be crosslinked.International monopoly WO 2009/060043 A2 discloses the method for photosensitive dose of stable ultrahigh molecular weight polyethylene(UHMWPE) of a kind of hindered amine, and this inhibitor is compared with vitamin E, has stronger anti-oxidant activity, and suppresses a little less than the crosslinked action.
In sum, the resistance of oxidation that adopts inhibitor to improve crosslinked ultra-high-molecular-weight polyethylene is a kind of effective means.Wherein, vitamin E is one of the most effective natural antioxidants.But vitamin E exists the limitation of self.Existing patent of invention is not all mentioned inhibitor beyond the vitamin E to the influence of ultrahigh molecular weight polyethylene(UHMWPE) and crosslinked ultra-high-molecular-weight polyethylene degree of crosslinking, resistance of oxidation, physical and mechanical properties.
In sum, existing crosslinked ultra-high-molecular-weight polyethylene is when obtaining excellent antiwear characteristic, and intensity and toughness significantly reduce.Use vitamin E can improve the oxidative stability of crosslinked polyethylene, but can suppress the raising of polyethylene crosslinking degree.
Summary of the invention
The objective of the invention is to deficiency, a kind of anti-oxidant cross-linked polymer is provided, and the preparation method of this anti-oxidant cross-linked polymer is provided to prior art.
Anti-oxidant cross-linked polymer of the present invention is that weight ratio is the crosslinked ultra-high-molecular-weight polyethylene of 100～10000:1 and the mixture of inhibitor, and the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 103～380mol/m
3, cross-linking density is that test obtains according to equilibrium swelling method (Muratoglu etc., Biomaterials 1,999 20 1463).
Described inhibitor is a coffic acid, gallic acid, a kind of in the Progallin LA.
This anti-oxidant cross-linked polymer has excellent resistance of oxidation, has higher degree of crosslinking and higher physical and mechanical properties simultaneously.
The concrete steps that prepare this anti-oxidant high cross-linked polymer method are:
Step (1). inhibitor added in the organic solvent mix; Form antioxidant solution; Again the polyvinyl resin with super-high molecular weight powder is added in the antioxidant solution; Descended dry 5～14 days at 40～80 ℃ behind the thorough mixing, obtain inhibitor/ultrahigh molecular weight polyethylene(UHMWPE) mix powder;
Every liter of organic solvent adds 50～200 gram inhibitors; Described inhibitor is a kind of in coffic acid, gallic acid, the Progallin LA; Described organic solvent is a kind of in acetone, ethanol, the sherwood oil;
Described polyvinyl resin with super-high molecular weight is that molecular weight is greater than 1,000,000 daltonian linear polyethylene resins;
The mass ratio of the polyvinyl resin with super-high molecular weight powder that adds and the inhibitor of adding is 100～10000:1;
Step (2). inhibitor/ultrahigh molecular weight polyethylene(UHMWPE) mix powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 180～240 ℃, be forced into 1～50 MPa, make the mix powder caking; Be cooled to 110～130 ℃ then, keep-uped pressure constant 0.5～72 hour, reduce to normal temperature again, obtain block blank after the demoulding;
Step (3). under the normal temperature, with block blank irradiation under 3～10MeV high-power electron beam, obtain 0.1～5 Mrad irradiation dose, total irradiation dose is 2.5～25Mrad at every turn, and irradiation dose is measured by standard irradiation colour developing film; Obtain oxidation resistant high cross-linked polymer behind the irradiation.In the irradiation process, the temperature of block blank raises to some extent, but the top temperature that can reach is lower than the fusing point of ultrahigh molecular weight polyethylene(UHMWPE), so material keeps crystalline state in the irradiation process.
Adopt the crosslinked ultra-high-molecular-weight polyethylene material of patent preparation of the present invention to have excellent abrasion resistance properties, oxidative stability, tensile strength and shock strength; Basically can not suppress crosslinked polymer; Thereby can not reduce the wear-resistant ability of cross-linked polymer, and have than with the stronger resistance of oxidation of equal size vitamin E.The inventive method does not need material is carried out any thermal treatment, thereby has guaranteed the excellent mechanical property of material.
The implantation of the inventive method preparation all is superior to containing the performance of the crosslinked ultra-high-molecular-weight polyethylene material of same vitamin E with high cross-linked polymer resistance of oxidation, degree of crosslinking, physical and mechanical properties; The performance that also is superior to the crosslinked ultra-high-molecular-weight polyethylene of irradiation and melting treatment; Can be used to make artificial joint spacer material; Comprise artificial hip joint liner and artificial knee joint platform, prepared joint prosthesis has longer expected service life.
Embodiment
Explain that below in conjunction with instance technical scheme of the present invention and effect further describe, used polyethylene resin powder is that molecular weight is greater than 1,000,000 daltonian linear polyethylene resins in following examples.
Embodiment 1.
Step (1). with mixing in 1 liter of alcohol solvent of 50 gram coffic acids addings, add 500 kilograms of polyethylene resin powder again, thorough mixing, 80 ℃ were descended dry 5 days, and obtained mix powder;
Step (2). mix powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 180 ℃, be forced into 50 MPa, make the mix powder caking; Be cooled to 110 ℃ then, keep-uped pressure constant 72 hours, reduce to normal temperature again, obtain block blank after the demoulding;
Step (3). under the normal temperature, with block blank irradiation under the 3MeV high-power electron beam, obtain 0.1 Mrad irradiation dose, total irradiation dose is 2.5Mrad at every turn, and irradiation dose is measured by standard irradiation colour developing film; Obtain oxidation resistant cross-linked polymer behind the irradiation, be designated as sample A.
Sample A is that weight ratio is crosslinked ultra-high-molecular-weight polyethylene and the caffeinic mixture of 10000:1; According to equilibrium swelling method (Muratoglu etc.; Biomaterials 1,999 20 1463) test, the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 103mol/m
3
Comparative example 1.
Step (1). with mixing in 1 liter of alcohol solvent of 50 gram vitamin E addings, add 500 kilograms of polyethylene resin powder again, thorough mixing, 80 ℃ were descended dry 5 days, and obtained mix powder;
Step (2). mix powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 180 ℃, be forced into 50 MPa, make the mix powder caking; Be cooled to 110 ℃ then, keep-uped pressure constant 72 hours, reduce to normal temperature again, obtain block blank after the demoulding;
Step (3). under the normal temperature, with block blank irradiation under the 3MeV high-power electron beam, obtain 0.1 Mrad irradiation dose, total irradiation dose is 2.5Mrad at every turn, and irradiation dose is measured by standard irradiation colour developing film; Obtain oxidation resistant high cross-linked polymer behind the irradiation, be designated as sample A1.
Sample A1 is that weight ratio is the crosslinked ultra-high-molecular-weight polyethylene of 10000:1 and the mixture of vitamin E, and according to the test of equilibrium swelling method, the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 98mol/m
3
Embodiment 2.
Step (1). with mixing in 1 liter of acetone solvent of 200 gram gallic acids addings, add 20 kilograms of polyethylene resin powder again, thorough mixing, 40 ℃ were descended dry 14 days, and obtained mix powder;
Step (2). mix powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 240 ℃, be forced into 1MPa, make the mix powder caking; Be cooled to 130 ℃ then, keep-uped pressure constant 0.5 hour, reduce to normal temperature again, obtain block blank after the demoulding;
Step (3). under the normal temperature, with block blank irradiation under the 10MeV high-power electron beam, obtain the 5Mrad irradiation dose, total irradiation dose is 25Mrad at every turn, and irradiation dose is measured by standard irradiation colour developing film; Obtain oxidation resistant high cross-linked polymer behind the irradiation, be designated as sample B.
Sample B is that weight ratio is the crosslinked ultra-high-molecular-weight polyethylene of 100:1 and the mixture of gallic acid, and according to the test of equilibrium swelling method, the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 346mol/m
3
Comparative example 2.
Step (1). with mixing in 1 liter of acetone solvent of 200 gram vitamin E addings, add 20 kilograms of polyethylene resin powder again, thorough mixing, 40 ℃ were descended dry 14 days, and obtained mix powder;
Step (2). mix powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 240 ℃, be forced into 1MPa, make the mix powder caking; Be cooled to 130 ℃ then, keep-uped pressure constant 0.5 hour, reduce to normal temperature again, obtain block blank after the demoulding;
Step (3). under the normal temperature, with block blank irradiation under the 10MeV high-power electron beam, obtain the 5Mrad irradiation dose, total irradiation dose is 25Mrad at every turn, and irradiation dose is measured by standard irradiation colour developing film; Obtain oxidation resistant high cross-linked polymer behind the irradiation, be designated as sample B1.
Sample B1 is that weight ratio is the crosslinked ultra-high-molecular-weight polyethylene of 100:1 and the mixture of vitamin E, and according to the test of equilibrium swelling method, the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 175mol/m
3
Embodiment 3.
Step (1). with mixing in 1 liter of petroleum ether solvent of 100 gram Progallin LAs addings, add the double centner polyethylene resin powder again, thorough mixing, 60 ℃ were descended dry 10 days, and obtained mix powder;
Step (2). mix powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 200 ℃, be forced into 10MPa, make the mix powder caking; Be cooled to 120 ℃ then, keep-uped pressure constant 24 hours, reduce to normal temperature again, obtain block blank after the demoulding;
Step (3). under the normal temperature, with block blank irradiation under the 5MeV high-power electron beam, obtain the 1Mrad irradiation dose, total irradiation dose is 5Mrad at every turn, and irradiation dose is measured by standard irradiation colour developing film; Obtain oxidation resistant high cross-linked polymer behind the irradiation, be designated as sample C.
Sample C is that weight ratio is the crosslinked ultra-high-molecular-weight polyethylene of 1000:1 and the mixture of Progallin LA, and according to the test of equilibrium swelling method, the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 201mol/m
3
Comparative example 3.
Step (1). with mixing in 1 liter of petroleum ether solvent of 100 gram vitamin E addings, add the double centner polyethylene resin powder again, thorough mixing, 60 ℃ were descended dry 10 days, and obtained mix powder;
Step (2). mix powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 200 ℃, be forced into 10MPa, make the mix powder caking; Be cooled to 120 ℃ then, keep-uped pressure constant 24 hours, reduce to normal temperature again, obtain block blank after the demoulding;
Step (3). under the normal temperature, with block blank irradiation under the 5MeV high-power electron beam, obtain the 1Mrad irradiation dose, total irradiation dose is 5Mrad at every turn, and irradiation dose is measured by standard irradiation colour developing film; Obtain oxidation resistant high cross-linked polymer behind the irradiation, be designated as sample C1.
Sample C1 is that weight ratio is the crosslinked ultra-high-molecular-weight polyethylene of 1000:1 and the mixture of vitamin E, and according to the test of equilibrium swelling method, the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 182mol/m
3
Embodiment 4.
Step (1). with mixing in 1 liter of alcohol solvent of 60 gram gallic acids addings; Form the gallic acid ethanolic soln; The polyethylene resin powder that is GUR4150 with 20 kilograms of trades mark again adds in the gallic acid ethanolic soln; Descended dry 12 days at 50 ℃ behind the thorough mixing, obtain gallic acid/polyethylene mixture powder;
Step (2). gallic acid/polyethylene mixture powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 190 ℃, be forced into 30 MPa, make the mix powder caking; Be cooled to 110 ℃ then, constant 3 hours of 30 MPa that keep-up pressure reduce to normal temperature again, obtain block blank after the demoulding;
Step (3). under the normal temperature, with block blank irradiation under the 10MeV high-power electron beam, obtain the 2.5Mrad irradiation dose, total irradiation dose is 15Mrad at every turn.The high crosslinked ultra-high-molecular-weight polyethylene goods that obtain are designated as D.
Sample D is that weight ratio is the crosslinked ultra-high-molecular-weight polyethylene of 333:1 and the mixture of gallic acid, and according to the test of equilibrium swelling method, the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 267mol/m
3
Comparative example 4.
Step (1). with mixing in 1 liter of alcohol solvent of 60 gram vitamin E addings; Form the vitamin E ethanolic soln; The polyethylene resin powder that is GUR4150 with 20 kilograms of trades mark again adds in the vitamin E ethanolic soln; Descended dry 12 days at 50 ℃ behind the thorough mixing, obtain vitamin E/polyethylene mixture powder;
Step (2). vitamin E/polyethylene mixture powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 190 ℃, be forced into 30 MPa, make the mix powder caking; Be cooled to 110 ℃ then, constant 3 hours of 30 MPa that keep-up pressure reduce to normal temperature again, obtain block blank after the demoulding;
Step (3). under the normal temperature, with block blank irradiation under the 10MeV high-power electron beam, obtain the 2.5Mrad irradiation dose, total irradiation dose is 15Mrad at every turn; Obtain high crosslinked ultra-high-molecular-weight polyethylene and be designated as D1.
Sample D1 is that weight ratio is the crosslinked ultra-high-molecular-weight polyethylene of 333:1 and the mixture of vitamin E, and according to the test of equilibrium swelling method method, the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 213mol/m
3
Embodiment 5.
Step (1). with mixing in 1 liter of acetone solvent of 50 gram Progallin LAs addings; Form the gallic acid acetone soln; The polyethylene resin powder that is GUR1020 with 250 kilograms of trades mark again adds in the gallic acid acetone soln; Descended dry 6 days at 70 ℃ behind the thorough mixing, obtain gallic acid/polyethylene mixture powder;
Step (2). gallic acid/polyethylene mixture powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 220 ℃, be forced into 10 MPa, make the mix powder caking; Be cooled to 130 ℃ then, keep-uped pressure constant 1 hour, reduce to normal temperature then, obtain block blank after the demoulding;
Step (3). under the normal temperature, with block blank irradiation under the 10MeV high-power electron beam, obtain the 0.5Mrad irradiation dose, total irradiation dose is 7.5Mrad at every turn; Obtain high crosslinked ultra-high-molecular-weight polyethylene, be designated as E.
Sample E is that weight ratio is the crosslinked ultra-high-molecular-weight polyethylene of 5000:1 and the mixture of Progallin LA, and according to the test of equilibrium swelling method, the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 223mol/m
3
Comparative example 5.
Step (1). with mixing in 1 liter of acetone solvent of 50 gram vitamin E addings; Form the vitamin E acetone soln; The polyethylene resin powder that is GUR1020 with 250 kilograms of trades mark again adds in the vitamin E acetone soln; Descended dry 6 days at 70 ℃ behind the thorough mixing, obtain vitamin E/polyethylene mixture powder;
Step (2). vitamin E/polyethylene mixture powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 220 ℃, be forced into 10 MPa, make the mix powder caking; Be cooled to 130 ℃ then, keep-uped pressure constant 1 hour, reduce to normal temperature then, obtain block blank after the demoulding;
Step (3). under the normal temperature, with block blank irradiation under the 10MeV high-power electron beam, obtain the 0.5Mrad irradiation dose, total irradiation dose is 7.5Mrad at every turn; Obtain high crosslinked ultra-high-molecular-weight polyethylene, be designated as E1.
Sample E1 is that weight ratio is the crosslinked ultra-high-molecular-weight polyethylene of 5000:1 and the mixture of vitamin E, and according to the test of equilibrium swelling method, the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 218mol/m
3
Embodiment 6.
Step (1). with mixing in 1 liter of petroleum ether solvent of 50 gram Progallin LAs addings; Form the Progallin LA petroleum ether solution; Be in the polyethylene resin powder adding Progallin LA petroleum ether solution of GUR1050 with the double centner trade mark again; Descended dry 10 days at 50 ℃ behind the thorough mixing, obtain Progallin LA/polyethylene mixture powder;
Step (2). Progallin LA/polyethylene mixture powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 200 ℃, be forced into 15 MPa, make the mix powder caking; Be cooled to 120 ℃ then, keep-uped pressure constant 1.5 hours, reduce to normal temperature then, obtain block blank after the demoulding;
Step (3). under the normal temperature, with block blank irradiation under the 8MeV high-power electron beam, obtain the 2.5Mrad irradiation dose, total irradiation dose is 20Mrad at every turn; Obtain crosslinked ultra-high-molecular-weight polyethylene, be designated as F.
Sample F is that weight ratio is the crosslinked ultra-high-molecular-weight polyethylene of 2000:1 and the mixture of Progallin LA, and according to the test of equilibrium swelling method, the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 380mol/m
3
Comparative example 6.
Step (1). with mixing in 1 liter of petroleum ether solvent of 50 gram vitamin E addings; Form the vitamin E petroleum ether solution; Be in the polyethylene resin powder adding vitamin E petroleum ether solution of GUR1050 with the double centner trade mark again; Descended dry 10 days at 50 ℃ behind the thorough mixing, obtain vitamin E/polyethylene mixture powder;
Step (2). vitamin E/polyethylene mixture powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 200 ℃, be forced into 15 MPa, make the mix powder caking; Be cooled to 120 ℃ then, constant 1.5 hours of 15 MPa that keep-up pressure reduce to normal temperature then, and obtaining thickness after the demoulding is the block blank of 4.5cm;
Step (3). under the normal temperature, with block blank irradiation under the 8MeV high-power electron beam, obtain the 2.5Mrad irradiation dose, total irradiation dose is 20Mrad at every turn; Obtain high crosslinked ultra-high-molecular-weight polyethylene, be designated as F1.
Sample F 1 is the crosslinked ultra-high-molecular-weight polyethylene of 2000:1 and the mixture of vitamin E for weight ratio, and according to the test of equilibrium swelling method, the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 311mol/m
3
Embodiment and comparative example product property are relatively
Can find out by above embodiment and comparative example; Compare with the crosslinked ultra-high-molecular-weight polyethylene that contains vitamin E; Contain the advantage that has several aspects behind the ultrahigh molecular weight polyethylene(UHMWPE) cross-linking radiation of coffic acid, gallic acid, Progallin LA: 1, anti-oxidant activity is superior to vitamin E, and 2, under identical irradiation dose, have higher degree of crosslinking; 3, higher tensile strength, 4, higher shock strength.Therefore, utilize the present invention technology, can obtain to have the more crosslinked ultra-high-molecular-weight polyethylene material of HS and toughness and resistance of oxidation, this material can be used for making the intraarticular implant, the work-ing life of raising joint prosthesis.
Claims (7)
1. an anti-oxidant cross-linked polymer is characterized in that this polymkeric substance is that weight ratio is the crosslinked ultra-high-molecular-weight polyethylene of 100～10000:1 and the mixture of inhibitor, and the cross-linking density of crosslinked ultra-high-molecular-weight polyethylene is 103～380mol/m
3
2. the described a kind of anti-oxidant cross-linked polymer of claim 1 is characterized in that described inhibitor is a coffic acid, gallic acid, a kind of in the Progallin LA.
3. the method for preparing anti-oxidant cross-linked polymer as claimed in claim 1 is characterized in that the concrete steps of this method are:
Step (1). inhibitor added in the organic solvent mix; Form antioxidant solution; Again the polyvinyl resin with super-high molecular weight powder is added in the antioxidant solution; Descended dry 5～14 days at 40～80 ℃ behind the thorough mixing, obtain inhibitor/ultrahigh molecular weight polyethylene(UHMWPE) mix powder;
Step (2). inhibitor/ultrahigh molecular weight polyethylene(UHMWPE) mix powder is placed mould, and place on the hot plate of vulcanizing press, be heated to 180～240 ℃, be forced into 1～50 MPa, make the mix powder caking; Be cooled to 110～130 ℃ then, keep-uped pressure constant 0.5～72 hour, reduce to normal temperature again, obtain block blank after the demoulding;
Step (3). under the normal temperature, with block blank irradiation under 3～10MeV electron beam, obtain 0.1～5 Mrad irradiation dose, total irradiation dose is 2.5～25Mrad, obtains oxidation resistant cross-linked polymer behind the irradiation at every turn.
4. the method for the anti-oxidant cross-linked polymer of preparation as claimed in claim 3; It is characterized in that: every liter of organic solvent adds 50～200 gram inhibitors in the step (1), and the mass ratio of the polyvinyl resin with super-high molecular weight powder of adding and the inhibitor of adding is 100～10000:1.
5. the method for the anti-oxidant cross-linked polymer of preparation as claimed in claim 3 is characterized in that: the inhibitor described in the step (1) is a kind of in coffic acid, gallic acid, the Progallin LA.
6. the method for the anti-oxidant cross-linked polymer of preparation as claimed in claim 3 is characterized in that: the organic solvent described in the step (1) is a kind of in acetone, ethanol, the sherwood oil.
7. the method for the anti-oxidant cross-linked polymer of preparation as claimed in claim 3 is characterized in that: the polyvinyl resin with super-high molecular weight described in the step (1) is that molecular weight is greater than 1,000,000 daltonian linear polyethylene resins.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102824232A (en) * | 2012-08-28 | 2012-12-19 | 中国科学院宁波材料技术与工程研究所 | Anti-oxidation artificial joint prosthesis and preparation method thereof |
| CN103007353A (en) * | 2012-12-24 | 2013-04-03 | 南京理工大学 | Ultrahigh-molecular weight polyethylene composite material for artificial joint and preparation method of ultrahigh-molecular weight polyethylene composite material |
| CN106633287A (en) * | 2016-11-29 | 2017-05-10 | 中广核三角洲（苏州）新材料研发有限公司 | Preparation method of wear-resistant heat-conducting irradiation-crosslinking ultra-high molecular weight polyethylene |
| CN107754013A (en) * | 2017-12-04 | 2018-03-06 | 四川大学 | The high crosslinked ultra-high-molecular-weight polyethylene artificial joint material of high antioxygen and preparation method |
| CN109535560A (en) * | 2018-11-29 | 2019-03-29 | 袁进 | A kind of TPV material and preparation method thereof haveing excellent performance |
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| CN111135343A (en) * | 2019-12-19 | 2020-05-12 | 江苏集萃先进高分子材料研究所有限公司 | High-crosslinking high-antioxidant-doped artificial joint prosthesis material and preparation method thereof |
| CN112870448A (en) * | 2021-01-19 | 2021-06-01 | 湖北大学 | Ultrahigh molecular weight polyethylene plate and preparation method and application thereof |
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| WO2023078167A1 (en) * | 2021-11-04 | 2023-05-11 | 苏州微创关节医疗科技有限公司 | Polyethylene joint implant and manufacturing method therefor, and joint prosthesis |
| WO2023078165A1 (en) * | 2021-11-02 | 2023-05-11 | 苏州微创关节医疗科技有限公司 | Ultrahigh molecular weight polyethylene implant and preparation method therefor, and artificial joint |
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| CN102824232B (en) * | 2012-08-28 | 2015-07-22 | 中国科学院宁波材料技术与工程研究所 | Anti-oxidation artificial joint prosthesis and preparation method thereof |
| CN102824232A (en) * | 2012-08-28 | 2012-12-19 | 中国科学院宁波材料技术与工程研究所 | Anti-oxidation artificial joint prosthesis and preparation method thereof |
| CN103007353A (en) * | 2012-12-24 | 2013-04-03 | 南京理工大学 | Ultrahigh-molecular weight polyethylene composite material for artificial joint and preparation method of ultrahigh-molecular weight polyethylene composite material |
| CN103007353B (en) * | 2012-12-24 | 2014-08-20 | 南京理工大学 | Ultrahigh-molecular weight polyethylene composite material for artificial joint and preparation method of ultrahigh-molecular weight polyethylene composite material |
| CN106633287A (en) * | 2016-11-29 | 2017-05-10 | 中广核三角洲（苏州）新材料研发有限公司 | Preparation method of wear-resistant heat-conducting irradiation-crosslinking ultra-high molecular weight polyethylene |
| CN107754013B (en) * | 2017-12-04 | 2020-11-10 | 四川大学 | High-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material and preparation method thereof |
| CN107754013A (en) * | 2017-12-04 | 2018-03-06 | 四川大学 | The high crosslinked ultra-high-molecular-weight polyethylene artificial joint material of high antioxygen and preparation method |
| CN109535560A (en) * | 2018-11-29 | 2019-03-29 | 袁进 | A kind of TPV material and preparation method thereof haveing excellent performance |
| CN111073004A (en) * | 2019-12-16 | 2020-04-28 | 四川大学 | Method for improving irradiation crosslinking density and oxidation stability of ultrahigh molecular weight polyethylene joint material |
| CN111135343A (en) * | 2019-12-19 | 2020-05-12 | 江苏集萃先进高分子材料研究所有限公司 | High-crosslinking high-antioxidant-doped artificial joint prosthesis material and preparation method thereof |
| CN112870448A (en) * | 2021-01-19 | 2021-06-01 | 湖北大学 | Ultrahigh molecular weight polyethylene plate and preparation method and application thereof |
| CN112980011A (en) * | 2021-03-23 | 2021-06-18 | 上海威高医疗技术发展有限公司 | Antioxidant gradient crosslinked polyethylene material and preparation method thereof |
| WO2023078165A1 (en) * | 2021-11-02 | 2023-05-11 | 苏州微创关节医疗科技有限公司 | Ultrahigh molecular weight polyethylene implant and preparation method therefor, and artificial joint |
| WO2023078167A1 (en) * | 2021-11-04 | 2023-05-11 | 苏州微创关节医疗科技有限公司 | Polyethylene joint implant and manufacturing method therefor, and joint prosthesis |
| CN114864163A (en) * | 2022-05-06 | 2022-08-05 | 湖北南远电缆科技有限公司 | High-temperature-resistant flame-retardant cable |
| CN114864163B (en) * | 2022-05-06 | 2022-12-30 | 湖北南远电缆科技有限公司 | High-temperature-resistant flame-retardant cable |
| CN117698248A (en) * | 2023-12-25 | 2024-03-15 | 宁波华寅包装科技有限公司 | Toughened puncture-resistant vacuum compression bag and preparation method thereof |
| CN117698248B (en) * | 2023-12-25 | 2024-05-24 | 宁波华寅包装科技有限公司 | Toughened puncture-resistant vacuum compression bag and preparation method thereof |
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